Pyrazolone azo dyestuffs and process for preparing the same



Patented Feb, 24, 1931 UlallTE HERMANN 'WAGNER, OF SODEN-GN-THE-T FISCHER, OF HGCI-ZSiT-GEE -l'1'ZAEN, G

ll/ HUS, AND HEINZ EICHHEDE AND ERICH WORKS, INC., 0]? NEW YORK, N. Y., A COBOEATION OF DELAWARE PYRAZOLONE AZO DYES'EJFFS AND PRGCESS FOR EREPAR-ING THE SAIVIE ()ur present invention relates to new pyrazolone azodyestufis and process for making the same.

We have found that valuable azo dyestuffs, which are suitable for the dyeing 0t fibers of all kinds or for use as color lakes, are obtainable by coupling any diam-compound with a compound of the general formula wherein X represents a methyl-, carboxylic acidor a carboxylic acid ester group. lhese compounds, which have not yet been described, are obtainable in the known manner by condensing toe hydrazine with acetoacetic ester or oXalacetic ester. Our new azo dyestutls correspond to the general formula RN=NCHO.X

HOa

wherein X represents a methyl-, carboxylic acidor a carboxylic acid ester group and R represents any aromatic nucleus substituted or not.

The following examples serve to illustrate our invention but they are not intended to limit it thereto, all parts being by weight.

1. 883.5 parts of the sodium salt of 1-(- chlor-5-methyl-2 sul'fophenyl) 5 pyrazolone-3-carboxylic acid ethylester are dissolved in water and mixed with an excess of a sodium acetate solution. Into the solution thus pre pared is run a diazo compound produced in No Drawing. Application filed November 15, 1926, Serial No. 148,605, and in Germany November 19, 1925.

the known manner from 1? 3 parts of orthoanilinesultonic acid. The dye-stud after being completely separated with potassium chloride, filtered and dried, forms a pure yellow powder which dyes wool a greenishyellow tint of excellent properties as to fast.- ness. It has the probable formula:

OsNa N NaOaS a 1]": the ethylester used in the above example is replaced by another ester, for instance NaOaS 3. 325.5 parts of the sodium salt of 1-H!- chlor 5-"nethyl-2 sulfophenyl) 3 methyl-5- pyrazolone are prepared for being coupled in the manner indicated in nxaanple 1. With this solution is combined a diazo solution, obtained in the usual manner from 207.5 parts of -chlor-1-aminobenzene-Q-sulfonic acid. The resulting dyestuff separates already during the couplin process and it also gives on wool a very fast greenish-yellow tint.

It has the probable formula:

1 0:0 N SOaNa. \N/

Naoas 4. A diazo solution obtained in the usual manner from 266 parts of 2-amino-l-toluene- 3.5-disulphonic acid is caused to act upon a solution of 355.5 parts of the sodium salt of 1- y-chlor 5 -methyl- 2-sulfophenyl) 5- pyrazolone-3-carboxylic acid produced according to Example 1. W'hen the coupling process is com alete, the dyestuff is separated by adding potassium chloride and dried. This dyestui'f dyes wool a greenish-yellow tint of excellent fastness to light.

It has the probable formula:

OaNa.

NaOaS The dyestuff is also suitable for being used as a lake-dye, which is, when prepared with barium sulfate, remarkable for its greenish tint.

5. In a tetrazo solution obtained in the known manner from 226 parts of 4.4 diaminodiphenyldimethylmethane, is combined with a solution of 661 parts of the sodium salt of 1- (et-chlor-5-methyl-2 -sulfophenyl) -3- methyl-S-pyrazolone, obtained according to Example 3 and Example 1 respectively, a yellow dyestulf is obtained which, owing to its good fastness to milling and washing, is particularly suitable for being used in the dyeing of yarn.

It has the probable formula:

. Instead of the diazo compound mentioned SOaH it 2. As a new product, the pyrazolone azodyestuif of the formula:

3. The process which comprises coupling any diazo compound with a compound of the general formula:

$0311 t N =0 XX I-(EH2 wherein X represents a methyL, carboxylic acidor a carboXylic acid ester group.

4:. The process which comprises diazotizing a compound of the general formula:

wherein Y represents hydrogen or a monovalent substituent and coupling the diazo compound thus obtained with a compound of the general formula:

wherein X represents a methyl-, carboxylic acid and a carboxyllc acid ester group.

5. The process which comprises diazotizmg a compound of the general formula:

wherein Z represents hydrogen or halogen and coupling the diazo compound thus obtained with a compound of the general formula:

wherein X represents a methyl-, carboxylic acid or a carboxylic acid ester group.

6. The process which comprises diazotizing a compound of the general formula:

SOIH

wherein Z represents hydrogen or halogen and coupling the diazo compound thus obtained with the compound of the probable formula:

N N/ =0 CHr- H5 5o 7 As new products the azo dyestuffs of the general formula:

RN=NCH-O.X

O=C N \N/ Ho's wherein X represents a methyL, carboxylic acidor a carboxylic acid ester group and R represents any aromatic nucleus substituted or not.

8. As new products the azo dyestuffs of the general formula:

HOaS

wherein Z represents hydrogen or halogen.

In testimony whereof, we aflix our signatures.

HERMANN WAGNER. HEINZ EICHWEDE. ERIGH FISCHER. 

